Azo dyestuff



Patented July 24, I934 UNITEo STATES Azo DYESTUFF t Gerhard Schrader,

Opladen,

and 1 1 Albert Schmelzer and Fritz Ballauf, Cologne-Mulheim,

, Germany, assignorsto Inc., New York, N. Y., ware v General Aniline Works, a corporation of Dela- 'No Drawing. Application July 15, 1931, Serial No.

551,049. In Germany July 19, 1930 SCIainis. (01; 260-86) v The present invention relates to azo dyestufl's, more particularly it relates to azo dyestuffs which may be represented by the probable general formula:

wherein fwfstands for hydrogen or an alkyl group, R stands for the radical of a'coupling component of the aromatic-, carbazole-, acetoacetic arlyamideand pyrazolone series, a stands for one of the numbers oneand two, alk stands fo'ran alkyl group, such as a methyl-, an ethylor abenz'yl group, and n stands for one of the numbers one 'aridtwo,

Our new dyestuiis are obtainable by diazotizing in the usual manner an aminoalkoxy-carbazole and coupling in substance, on a substratum or on a fibre with a coupling component suitable for producing azo dyestufis, such as 2.3-hydro xy naphthoic acid arylamides, pyrazolones, acetoacetic acid arylamides, phenols of 'thebenzone or naphthalen'e f series-and their "sulfonic acids, hydroxycarbazoles and the like.

Our new dyestuffs'are generallyldark, metallic lustrous powders, dyeing the cellulosic fibre generally violet to blueto black shades.

The starting amino-alkoxy-carbazoles are obtainable by nitrating the corresponding N-acetylalkoxyf'carbazoles and reducing the :nitro group or groups, the splitting ofi of the acetyl group simultaneously taking place in the reduction; this processof preparing the dia'aotization component is more fully describedin our co-pending' application" for Letters Patent SerialNo.551,048, filed July. 1591931, entitled; New substituted alkoxycarba'zolesi The invention-is""illustrateda by the following examples, withoutbeing' limited thereto:

Example 1.--Well boiledand dried cotton yarn is impregnated with a" solution of 3.5 grams of 2-naphthol-3-carboxy1ic acid anilide, 6 ccs. of

caustic 'soda lye (36 B.) and 6 ccs. ;of Turkey red oil per litre wrung out and without being drieddeveloped by means of a diazo solution containing 2512 wgramsgof 3- amino- 2methoxy car bazole per litre previously renderedacid to acetic acid by the addition of sodium acetate, rinsed and soaped. In this manner a beautiful blue is ob- I tained. The dyestuff has the following formula:

Example 2. --Well boiled cotton yarn isimpregnated .with asolution of 2:5grams of 2.3-hydroxynaphthoic acid'fi-naphthylamide; 8 cos. of Turkey-red oil and 5 cos. of; caustic soda lye (36 Be.) per litre and well wrung out. 24.0 parts by Weight of 3 an ino=2-ethoxygQemethyhcarbazole"'(obtained by' methylating 3-nitro-2-ethoxy-carbazolef with dimeth'yl sulfate in alcoholic alkaline solutionwith subsequent reduction) are diazotized in a sufiicient quantity of dilute hydrochloricv acid with 7 parts by weight of sodium nitrite, and the. diazo solution is diluted to a concentration of 1/100 mol per litre. j

In this solution: of diaz'otized 3. -amino-2- ethoxy-9-methyl-carbazole neutralized with sodium acetate the grounded cotton yarn is developed. "After rinsing and soaping, a blackish blue o'f v e ry good fastness to boiling is obtained. The dyestuff corresponds to the following iormulaz-- g p u pregnated with this solution, wrung out and introduced into a diazo solution neutralized by the addition of sodium acetate and containing in a litre the diazonium compound from 2.12

5 grams of 6-amino-3-methoXy-carbazole for about 20 minutes, rinsed and soaped. In this manner a clear, bluish-violet is obtained. The dyestuff has the following formula:

N= OCHr I 1 00 OH Example 4.2,4 grame of 2 hy droxy tar-benzecarbazole are made into a paste with 5 cos. of caustic soda lye (36 B.) dissolved with hot .water and' the solution is made up with waterto one litre.

50 grams of cotton yarn are impregnated with this solution, wrung out and introduced into a diazo solution neutralized by the addition of sodium acetate and containing in a litre 1,4 grams of 1.8-diethoxy-3.6-diaminocarbazole, rinsed and soaped. In this'manner a dark, bluish-blackis obtained. The dyestufi has the following formula:

NH: N:

H I OfozHs" Q. Example 5.--Well boiled and dried cotton yarn is impregnated with a. solution containing per litre 2,9 grams of Z-hydrOXyphenanthrene, 6 cos. of Turkey red'oil and 5 cos. of causic soda lye (36 B.) and wrung out. Then the grounded cot-. ton yarn is developed with a diazosolution'cone taining in a litre 2,8 grams of 3-amin'o-2ehydroxycarbazole-benzylether. After rinsing and soaping a strong, bluish-violetis obtained. Thedyestuff corresponds to the following formula:

wherein :a:" stands for hydrogen or an alkyl group, alk' stands fo r'an alkyl group, R stands for the radical of a coupling component of the aromatic-,: carbazole-, acetoacetic arylamide-and group, the z and the characters 2 stand for pyrazolone series wherein n and 11' stand for one of the numbers one and two, being generally dark, metallic lustrous powders and dyeing the cellulosic fibre generally violet to blue to black shades.

2. Azo dyestuffs of the general formula:

. u N=NR V \N z v wherein :0 stands for hydrogen or an alkyl hydrogen or alkoxy in such a manner that in case the characters. 2 mean hydrogen 2' means alkoxy and vice versa, R stands for the radical of a 2.3-hydroxynaphthoic acid arylamide, and y stands for hydrogen or N=N-R, being generally dark, metallic lustrous powders and dyeing the cellulosic fibre generally blue to violet shades.

3. Azo dyestuffs of the general formula:

H wheremfialk stands for an alkyl group and R stands for the radical of a 2.3-hydroxynaphthoic acid arylamide, being generally dark, metallic lustrous powders and dyeing the cellulosic fibre generally blue to violet shades.

4. The azo dyestuff of the following formula:

. DO\N being a dark, metallic lustrous powder and dyeing the'cellulosic fibre blue shades.

5. Azo dyestuffs of the general formula:

N 0 -alk wherein alkfstand for alkyl groups andR. stands for the radical of a 2.3-hydroxynaphthoic vacid arylamide, being generally dark, metallic lustrous powders,and dyeing the cellulosic fibre generally blue to violet shades.

6. The azo dyestuff of the following formula:

being a dark, metallic lustrous powder and dyeing the cellulosic fibre blackish-blue shades. 7. A20 dyestuffs of the general formula:

8. The azo dyestufi' of the following formula:

OOH:

being a dark, metallic lustrous powder, and dyeing the cellulosic fibre bluish-violet shades.

GERHARD SCHRADER. ALBERT SCHMELZER. FRITZ BALLAUF. 

